Photo-oxidation of Micro- and Nanoplastics: Physical, Chemical, and Biological Effects in Environments.

Micro- and nanoplastics (MNPs) are attracting increasing attention due to their persistence and potential ecological risks. This review critically summarizes the effects of photo-oxidation on the physical, chemical, and biological behaviors of MNPs in aquatic and terrestrial environments. The core of this paper explores how photo-oxidation-induced surface property changes in MNPs affect their adsorption toward contaminants, the stability and mobility of MNPs in water and porous media, as well as the transport of pollutants such as organic pollutants (OPs) and heavy metals (HMs). It then reviews the photochemical processes of MNPs with coexisting constituents, highlighting critical factors affecting the photo-oxidation of MNPs, and the contribution of MNPs to the phototransformation of other contaminants. The distinct biological effects and mechanism of aged MNPs are pointed out, in terms of the toxicity to aquatic organisms, biofilm formation, planktonic microbial growth, and soil and sediment microbial community and function. Furthermore, the research gaps and perspectives are put forward, regarding the underlying interaction mechanisms of MNPs with coexisting natural constituents and pollutants under photo-oxidation conditions, the combined effects of photo-oxidation and natural constituents on the fate of MNPs, and the microbiological effect of photoaged MNPs, especially the biotransformation of pollutants.

Effluent toxicity study using biomarkers for ciprofloxacin photoelectrocatalytic degradation by bismuth-doped titanium dioxide nanotubes.

Ciprofloxacin hydrochloride (CIP) is a broad-spectrum synthetic antibiotic often found in domestic sewage and industrial waste due to the inefficiency of conventional treatments. Given the potential risk of drug accumulation, this study presents coatings of titanium dioxide nanotubes (TiO2) doped with different bismuth (Bi) concentrations to degrade CIP through photocatalytic and photoelectrochemical processes. Characterization studies revealed that bismuth (Bi) doping affected the morphology of the materials, with concentrations of 0.01 and 0.05 mol L-1, resulting in collapsed materials with a smaller active surface area. Photocatalysis tests for all the materials exhibited a similar degree of efficiency to photolysis, approximately 33%. Ecotoxicity tests using the biomarkers Lactuca sativa L., Lemna minor, and Artemia salina indicated that, although they were similar to photolysis in terms of efficiency, the effluents generated when employing the doped catalysts showed lower levels of toxicity, with the best results achieved for the material doped with 0.005 mol L-1 of Bi, with a toxicity level approximately 40% lower. Photoelectrocatalysis proved to be the most efficient CIP degradation technique. The highest degradation rate was observed for materials doped with 0.005 mol L-1 of Bi, with an efficiency of 46%, which is 1.4 times more efficient than photolysis. These results demonstrate that materials doped with low amounts of Bi can be effectively used as photoanodes for drug degradation, as their performance is superior, and the final product generated exhibits low toxicity to living organisms.

Photochemical Metallization: Advancements in Polypropylene Surface Treatment.

The work was devoted to the development of technology for applying metal coatings to the surface of polypropylene products. At the same time, the main stages of the technology were carried out using the influence of electromagnetic waves of light radiation. So, to obtain an electrically conductive silver layer, after mechanical treatment, etching and activation, the polymer was immersed for several minutes in a solution containing 10-20 g/L of silver nitrate and equivalent amounts of ascorbic acid, and a thin layer of solution was obtained on the surface of the polymer. A sample with such a sorption film was exposed to electromagnetic waves of light radiation at a flux density of 700-1100 W/m2. The small thickness of the sorption film facilitated the penetration of these waves directly onto the polymer surface and ensured the photochemical process of silver reduction with the formation of active centers. At the same time, electromagnetic waves acting on ascorbic acid transferred it to an excited state. As a result, the chemical reduction of silver in the space between the active centers became possible. In this case, the film obtained within 15-20 min had the necessary electrical conductivity. The suitability of these films for galvanic metallization of the polymer surface was shown.

A vehicle-mounted dual-smog chamber: Characterization and its preliminary application to evolutionary simulation of photochemical processes in a quasi-realistic atmosphere.

Smog chambers are the effective tools for studying formation mechanisms of air pollution. Simulations by traditional smog chambers differ to a large extent from real atmospheric conditions, including light, temperature and atmospheric composition. However, the existing parameters for mechanism interpretation are derived from the traditional smog chambers. To address the gap between the traditional laboratory simulations and the photochemistry in the real atmosphere, a vehicle-mounted indoor-outdoor dual-smog chamber (JNU-VMDSC) was developed, which can be quickly transferred to the desired sites to simulate quasi-realistic atmosphere simultaneously in both chambers using "local air". Multiple key parameters of the smog chamber were characterized in the study, demonstrating that JNU-VMDSC meets the requirements of general atmospheric chemistry simulation studies. Additionally, the preliminary results for the photochemical simulations of quasi-realistic atmospheres in Pearl River Delta region and Nanling Mountains are consistent with literature reports on the photochemistry in this region. JNU-VMDSC provides a convenient and reliable experimental device and means to study the mechanism of atmospheric photochemical reactions to obtain near-real results, and will make a great contribution to the control of composite air pollution.

Global Corrections to Reference Irradiance Spectra for Non-Clear-Sky Conditions.

Photochemical reactions in surface waters play important roles in element cycling and in the removal of organic contaminants, among other processes. A central environmental variable affecting photochemical processes in surface waters is the incoming solar irradiance, as this initiates these processes. However, clear-sky incident irradiance spectra are often used when evaluating the fate of aquatic contaminants, leading to an overestimation of contaminant decay rates due to photochemical transformation. In this work, incident irradiance satellite data were used to develop global-scale non-clear-sky correction factors for commonly used reference irradiance spectra. Non-clear-sky conditions can decrease incident irradiance by over 90% depending on the geographic location and time of the year, with latitudes above 40°N being most heavily affected by seasons. The impact of non-clear-sky conditions on contaminant half-lives was illustrated in a case study of triclosan in lake Greifensee, which showed a 39% increase in the triclosan half-life over the course of a year under non-clear-sky conditions. A global annual average correction factor of 0.76 was determined as an approximate way to account for non-clear-sky conditions. The correction factors are developed at monthly and seasonal resolutions for every location on the globe between 70°N and 60°S at a 4 km spatial resolution and can be used by researchers, practitioners, and regulators who need improved estimates of incident irradiance.

Highlighting nuances of blue light phototherapy: Mechanisms and safety considerations.

The efficacy of blue light therapy in dermatology relies on numerous clinical studies. The safety remains a topic of controversy, where potentially deleterious effects were derived from in vitro rather than in vivo experiments. The objectives of this work were (1) to highlight the nuances behind "colors" of blue light, light propagation in tissue and the plurality of modes of action; and (2) to rigorously analyze studies on humans reporting both clinical and histological data from skin biopsies with focus on DNA damage, proliferation, apoptosis, oxidative stress, impact on collagen, elastin, immune cells, and pigmentation. We conclude that blue light therapy is safe for human skin. It induces intriguing skin pigmentation, in part mediated by photoreceptor Opsin-3, which might have a photoprotective effect against ultraviolet irradiation. Future research needs to unravel photochemical reactions and the most effective and safe parameters of blue light in dermatology.

Hydrated electron based photochemical processes for water treatment.

Hydrated electron (eaq-) based photochemical processes have emerged as a promising technology for contaminant removal in water due to the mild operating conditions. This review aims to provide a comprehensive and up-to-date summary on eaq- based photochemical processes for the decomposition of various oxidative contaminants. Specifically, the characteristics of different photo-reductive systems are first elaborated, including the environment required to generate sufficient eaq-, the advantages and disadvantages of each system, and the comparison of the degradation efficiency of contaminants induced by eaq-. In addition, the identification methods of eaq- (e.g., laser flash photolysis, scavenging studies, chemical probes and electron spin resonance techniques) are summarized, and the influences of operating conditions (e.g., solution pH, dissolved oxygen, source chemical concentration and UV type) on the performance of contaminants are also discussed. Considering the complexity of contaminated water, particular attention is paid to the influence of water matrix (e.g., coexisting anions, alkalinity and humic acid). Moreover, the degradation regularities of various contaminants (e.g., perfluorinated compounds, disinfection by-products and nitrate) by eaq- are summarized. We finally put forward several research prospects for the decomposition of contaminants by eaq- based photochemical processes to promote their practical application in water treatment.

Chlorophyll Fluorescence Imaging as a Tool for Evaluating Disease Resistance of Common Bean Lines in the Western Amazon Region of Colombia.

The evaluation of disease resistance is considered an important aspect of phenotyping for crop improvement. Identification of advanced lines of the common bean with disease resistance contributes to improved grain yields. This study aimed to determine the response of the photosynthetic apparatus to natural pathogen infection by using chlorophyll (Chla) fluorescence parameters and their relationship to the agronomic performance of 59 common bean lines and comparing the photosynthetic responses of naturally infected vs. healthy leaves. The study was conducted over two seasons under acid soil and high temperature conditions in the western Amazon region of Colombia. A disease susceptibility index (DSI) was developed and validated using chlorophyll a (Chla) fluorescence as a tool to identify Mesoamerican and Andean lines of common bean (Phaseolus vulgaris L.) that are resistant to pathogens. A negative effect on the functional status of the photosynthetic apparatus was found with the presence of pathogen infection, a situation that allowed the identification of four typologies based on the DSI values ((i) moderately resistant; (ii) moderately susceptible; (iii) susceptible; and (iv) highly susceptible). Moderately resistant lines, five of them from the Mesoamerican gene pool (ALB 350, SMC 200, BFS 10, SER 16, SMN 27) and one from the Andean gene pool (DAB 295), allocated a higher proportion of energy to photochemical processes, which increased the rate of electron transfer resulting in a lower sensitivity to disease stress. This photosynthetic response was associated with lower values of DSI, which translated into an increase in the accumulation of dry matter accumulation in different plant organs (leaves, stem, pods and roots). Thus, DSI values based on chlorophyll fluorescence response to pathogen infection could serve as a phenotyping tool for evaluating advanced common bean lines. Six common bean lines (ALB 350, BFS 10, DAB 295, SER 16, SMC 200 and SMN 27) were identified as less sensitive to disease stress under field conditions in the western Amazon region of Colombia, and these could serve as useful parents for improving the common bean for multiple stress resistance.

Quantifying the relative contributions of aqueous phase and photochemical processes to water-soluble organic carbon formation in winter in a megacity of South China.

To identify potential formation mechanisms of water-soluble organic carbon (WSOC) and quantify their contributions to WSOC in urban Guangzhou of south China, a comprehensive campaign was carried out in winter of 2019-2020. During the campaign, WSOC, total carbon (TC), black carbon (BC), water-soluble inorganic ions (WSIIs) and fourteen elements in PM2.5 were collected using inline instruments. Bulk PM2.5 and size-segregated particle samples were also synchronously collected using offline instruments for analyzing the dominant chemical components including WSOC, organic carbon (OC), elemental carbon (EC) and WSIIs. In addition, gaseous pollutants (e.g., NH3, SO2, HNO3, NO2, O3) and meteorological parameters were also measured during the same period. PM2.5 pollution episodes during the campaign period were mainly driven by increased nitrate concentrations. The mass concentration of WSOC increased from 3.9 ± 1.1 µg m-3 on non-episode days to 6.8 ± 0.6 µg m-3 on episode days, although the mass ratio of WSOC to OC in PM2.5 changed little (<4%). Photochemical processes dominated WSOC formation in the afternoon and aqueous phase chemical processes played the dominant role in the night, from which newly formed WSOC distributed in the condensation mode and the droplet mode, respectively. Source apportionment analysis using positive matrix factorization (PMF) model suggested that on average 35% and 65% of WSOC mass in PM2.5 were related with the photochemical processes and aqueous phase chemical processes, respectively. Aqueous phase chemical processes were highly affected by nitrate pollution, which was closely related with O3 pollution.

LED irradiated photo-Fenton for the removal of estrogenic activity and endocrine disruptors from wastewater treatment plant effluent.

The goal of this work was to evaluate the performance of the LED irradiated photo-Fenton process on the removal of (i) estrogenic activity and (ii) seven endocrine disruptors (EDs) (4-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17ß-estradiol, 17α-ethinylestradiol, and estriol) from real wastewater treatment plant effluent (WWTPE). EDs are a group of contaminants of emerging concern present in WWTPE and which may be recognized by hormone receptors, thus harming animal and human health. The yeast estrogenic screen test (YES) was used to quantify estrogenic activity promoted by EDs in WWTPE samples before and after photo-Fenton treatment. Tests were performed following a factorial design with different iron (20, 40, and 60 mg L-1) and hydrogen peroxide (100, 200, and 300 mg L-1) concentrations in a laboratory scale LED photoreactor (λ = 455 nm, 1.5 L, 1.6 × 10-6 Einstein s-1). EDs were analyzed by gas chromatography coupled to a mass spectrometer. Control experiments consisted of Fenton process, iron only, LED irradiation only, and H2O2 only. Optimum experimental conditions for LED photo-Fenton resulted in 62% removal of estrogenic activity and 59% mineralization. In addition, treated WWTPE was not toxic to Aliivibrio fischeri and more than 80% of EDs were removed during LED irradiated photo-Fenton. Although Fenton process showed similar efficiency to that obtained by LED photo-Fenton, a higher volume of sludge was generated in the dark. Finally, results obtained in this study confirm the applicability of LED irradiated photo-Fenton process for improving the quality of WWTPE as an alternative to solar photo-Fenton in case solar radiation is not available, thus reducing hazards associated to WWTPE reuse or discharge.

Degradation of Antibiotics in Wastewater: New Advances in Cavitational Treatments.

Over the past few decades, antibiotics have been considered emerging pollutants due to their persistence in aquatic ecosystems. Even at low concentrations, these pollutants contribute to the phenomenon of antibiotic resistance, while their degradation is still a longstanding challenge for wastewater treatment. In the present literature survey, we review the recent advances in synergistic techniques for antibiotic degradation in wastewater that combine either ultrasound (US) or hydrodynamic cavitation (HC) and oxidative, photo-catalytic, and enzymatic strategies. The degradation of sulfadiazine by HC/persulfate (PS)/H2O2/α-Fe2O3, US/PS/Fe0, and sono-photocatalysis with MgO@CNT nanocomposites processes; the degradation of tetracycline by US/H2O2/Fe3O4, US/O3/goethite, and HC/photocatalysis with TiO2 (P25) sono-photocatalysis with rGO/CdWO4 protocols; and the degradation of amoxicillin by US/Oxone®/Co2+ are discussed. In general, a higher efficiency of antibiotics removal and a faster structure degradation rate are reported under US or HC conditions as compared with the corresponding silent conditions. However, the removal of ciprofloxacin hydrochloride reached only 51% with US-assisted laccase-catalysis, though it was higher than those using US or enzymatic treatment alone. Moreover, a COD removal higher than 85% in several effluents of the pharmaceutical industry (500-7500 mg/L COD) was achieved by the US/O3/CuO process.

One-Pot Synthesis of Star Copolymers by the Combination of Metal-Free ATRP and ROP Processes.

A completely metal-free strategy is demonstrated for the preparation of star copolymers by combining atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) for the syntheses of block copolymers. These two different metal-free controlled/living polymerizations are simultaneously realized in one reaction medium in an orthogonal manner. For this purpose, a specific core with functional groups capable of initiating both polymerization types is synthesized. Next, vinyl and lactone monomers are simultaneously polymerized under visible light irradiation using specific catalysts. Spectral and chromatographic evidence demonstrates the success of the strategy as star copolymers are synthesized with controlled molecular weights and narrow distributions.

Photophysical and photochemical insights into the photodegradation of sulfapyridine in water: A joint experimental and theoretical study.

For organic pollutants, photodegradation, as a major abiotic elimination process and of great importance to the environmental fate and risk, involves rather complicated physical and chemical processes of excited molecules. Herein, we systematically studied the photophysical and photochemical processes of a widely used antibiotic, namely sulfapyridine. By means of density functional theory (DFT) computations, we examined the rate constants and the competition of both photophysical and photochemical processes, elucidated the photochemical reaction mechanism, calculated reaction quantum yield (Φ) based on both photophysical and photochemical processes, and subsequently estimated the photodegradation rate constant. We further conducted photolysis experiments to measure the photodegradation rate constant of sulfapyridine. Our computations showed that sulfapyridine at the lowest excited singlet state (S1) mainly undergoes internal conversion to its ground state, and is difficult to transfer to the lowest excited triplet states (T1) via intersystem crossing (ISC) and emit fluorescence. In T1 state, compared with phosphorescence emission and ISC, chemical reaction is much easier to initiate. Encouragingly, the theoretically predicted photodegradation rate constant is close to the experimentally observed value, indicating that quantum chemistry computation is powerful enough to study photodegradation involving ultra-fast photophysical and photochemical processes.

Advanced Photonic Processes for Photovoltaic and Energy Storage Systems.

Solar-energy harvesting through photovoltaic (PV) conversion is the most promising technology for long-term renewable energy production. At the same time, significant progress has been made in the development of energy-storage (ES) systems, which are essential components within the cycle of energy generation, transmission, and usage. Toward commercial applications, the enhancement of the performance and competitiveness of PV and ES systems requires the adoption of precise, but simple and low-cost manufacturing solutions, compatible with large-scale and high-throughput production lines. Photonic processes enable cost-efficient, noncontact, highly precise, and selective engineering of materials via photothermal, photochemical, or photophysical routes. Laser-based processes, in particular, provide access to a plethora of processing parameters that can be tuned with a remarkably high degree of precision to enable innovative processing routes that cannot be attained by conventional approaches. The focus here is on the application of advanced light-driven approaches for the fabrication, as well as the synthesis, of materials and components relevant to PV and ES systems. Besides presenting recent advances on recent achievements, the existing limitations are outlined and future possibilities and emerging prospects discussed.

Optograms and criminology: science, news reporting, and fanciful novels.

A persistent nineteenth-century urban legend was the notion that photograph-like images of the last-seen object or person would be preserved in the eyes of the dead. This popular notion followed technological developments (the daguerreotype and ophthalmoscope) that antedated by decades a basic understanding of retinal physiology. From 1876 to 1877, Boll described photochemical bleaching of the retina and produced a crude retinal image that remained briefly visible after death in an experimental animal. From 1877 to 1881, Kühne elaborated the processes involved in photochemical transduction, and created more complex retinal images, or "optograms," that were visible after the death of experimental animals under special laboratory circumstances. In 1880, Kühne reported the first human "optogram" when he examined the eyes following the state execution of a convicted murderer. Although the work of these physiologists increased public interest in "optography" as a potential tool in forensic investigations, Kühne and his student, Ayres, concluded after an extensive series of investigations that optography would never be useful for this purpose. Nevertheless, because of the prior tantalizing results, optography became a frequent consideration in speculative news reports of sensational unsolved murders, and as a plot device in works of fiction, some quite fantastical. Fictional portrayals included works by Rudyard Kipling and Jules Verne. Despite denouncement of optography for forensic investigations by Kühne, and by numerous physicians, the general public and mass media continued to press for examination of the retinae of murder victims well into the twentieth century, particularly in high-profile unsolved cases.

Evaluation of effects of photooxidized Vespa orientalis venom on memory and learning in rats

Wasp venom is mixture of complex proteins that have several physical and pharmacological properties. The photochemical detoxification of Vespa orientalis venom is expected to generate photooxidized venom sac extract (PVSE). Antigenically active PVSE is obtained by exposing the venom sac extract (VSE) of Vespa orientalis to ultraviolet radiation in the presence of methylene blue. The aim of the present work was to evaluate the effect of PVSE on learning and memory of rats. Detoxification of PVSE was evident since treated mice had longer survival time than the group of mice treated with VSE. Photooxidized VSE of V. orientalis revealed enhancement on learning and memory by shortening the time to reach food (TRF) in T-maze. In a 28-day study with rats, we observed that PVSE significantly decreased transfer latency (TL) in elevated plus maze (EPM), significantly increased step down latency (SDL), diminished step down errors (SDE) and time spent in shock zone (TSS) in step down avoidance test. Thus, we concluded that although there is a possibility of employing PVSE in the treatment of Alzheimer, dementia or neurodegenerative illness as a non-herbal and non-synthetic alternative for patients who do not respond to available therapy, further investigation is still required.(AU)